Method fob solubilizing at least



Patented Sept. 18, 1951 STA ES. ENT

O FICE ascasso METHOD FOR SOLUBILIZING. AT LEAST PARTIALLY INSOLUBLE AND. QELAT YIZED WAX S Manlfir onstein, N ew York, N.

No Drawing. ApplicationJulyB, 1949, Serial No. 103,753

3 Claims, (01. -231 1 This invention relates to the solubilizing of insoluble and gelatinized, or at least partially insoluble o partially gelatiniz ed, wax-typeesters as they are generally known in the, art;' thatfis higher fatty acid esters of high atomic polyand synthetically produced, oil-like esters of a higherfatty acid which comprises melting and compoundin with said oil, a compound come prising a metal, soap of a'com'pound selected fromfthe group consisting of higher fatty acids, higher fatty, acid esters, petroleum acids and resin acids, at a melting temperature below the decomposition, temperature of the. resulting compgsition and at such melting temperature, that substantially the entire 'rnassv of the resulting composition is melted into the liquid, stage; whereby to form a soluble fixed oil reaction product which is capable of forming a stable solution. This application, Serial No, 748,655 is in'turn a continuation-in-part oi my abandoned application Serial No.4 9 6 ,'262.

"Reference is hereby made to my pending, ap; pliea tion Serial No. 33,676, wherein I have dis,- closed and claimed a method of insohrbilizing andsolidifyingiatty acid esters of alcohols which comprises, treating said esters with a potentially, freefoizygen-yielding compound incapable of forming. a' metal soap with saidesters, at a tem perature sufficiently elevated to effect release of d, fi s QX e n ai er w reb to r a so idi ed. qo npo t w h is n qlu e n, c tar and petroleum solvents. Thus in, the latter.

application, Serial No. 33,676, I have disclosed that the formation of an at least partially in soluble state is. not limited to the polyh'ydroxyl alcohol fatty acid esters (having more than, two OHIgroups) oi the, type disclosed in Serial No.

7433,6615, but I have additionally disclosed a 1 39 ess for at least partially solidifying s'ueh products which are derived fromalcohols havinglessthan 3 ms-W s t l l as consisting chiefly of higher fatty acidesters Thus the present application presents a process for solubilizing and utilizing the esters, of

polyhydroxyl alcohols having less than three hy;

droxylgroups. More specifically, the present application is. primarily concerned with the solubilization of a class, of. natural and synthetic substances knownas waxes. It is diflicultto, specifically, define. a wax because of the range of products to which the term is applied, although for present purposes the waxes may be regarded of mono and dihydroxy high atomic'alcohols, associated with onefor more of the free fat and wax acids, free monohydric alcohols andsterols, hydrocarbons, and lactones or other condensation compounds. See The Chemistry and Technology of Waxes byWarth, 1951.7.

Thus, wax-forming esters such as cetyl palmitate are regarded as waxes. Waxes are generally referred to as being of insect, vegetable,

animal, semi-mineral or mineral origin. The waxes of mineral origin are known as unsaponi fiable waxes which consist largely of hydrocarbons; e. g, ozokerite and ceresin. The mineral waxes and paraff n waxes consist of a group of hydrocarbons related to methane and are there; fore: not properly definable as waxes in that they do not consist primarily of higher fatty acid esters of monoor dihydric high atomic alcohols andhigher fatty acids.

In contrast to these unsaponifiable hydrocarbon mineral waxes, the waxes generally known as semi-mineral waxes com rise mostly esters of high molecular weight alcohols and acids, plus free acids. Accordingly, the semirmineral waxes,

such as montan wax, are more properly classifiable as natural vegetable type waxes'such as carnauba or candelill'a type waxes which are incompletely saponified with alkali (see page 6' of the booklet Waxes by American Cyan'a'mid and Accordingly, semi-mineral Chemical Corp), wakes 0f the montan type come'within the purview of the present invention; whereas, mineral and parafiinwagces do not come within the purview of the present invention.

It is known that the most desirablebases for use in preparing coating compositions are those which, produce coatings having a minimum degree of; swelling. The swelling capacity-of amaterial is characterized by the fact that the swelling is connected with an increased in volume and. the deswelling; i. e., shrinking, is connected with adecrease in volume. Thusfit is general practiee in the coating art to avoidthe use of varnishes, oils, lacquers, or similar compounds asserts which are in a swollen condition. For example, waxes which can be readily transformed as by polymerization, or by the application of heat, by distillation or by chemical action into a partially insoluble condition and having some swelling ability, are enerally used in a non-gelatinous condition. Thus gelatinized waxes have heretofore been of little use in the coating arts.

It has been observed that such materials which are used in a swollen condition, as for instance highly polymerized waxes, undergo shrinking while drying and that during the drying or in the shrunken condition, such materials lose most of their abilit to swell, probably by virtue of oxidation, polymerization or other chemical ac- 1 tion. One possible explanation is that the components of such materials are apparently connected to each other in a special manner and in a different manner than are the molecules of other materials which are readily soluble in the usual thinners or varnish solvents.

An object of the present invention is to provide a process for treating at least partially insoluble, gelatinous, swollen waxes so that they are capable of being applied by coating or covering methods, as by brushing, spraying, dipping, or extruding, and can further be compounded without the necessity of being returned to a nonswelling condition.

Another object of the invention is to provide a'process for the preparation of a stable, soluble wax base composition having a high shrinkage capacity when dried from a state of solution.

' A further object of the invention is to provide a process for solubilizing a swelled, at least partially insoluble, gelatinous wax base composition.

Still another object of the invention is to provide a process for'modifying the coating characteristics of waxes so as to bring then into a swelling or swollen condition where they can be readily worked up or dissolved into a liquid state, and in which condition they can be stored indefinitely and then can be used directl and can be readily worked upor dissolved into a liquid state, and in which condition they can be stored indefinitely and then can be used directly and can be readily diluted for use as a coating composition.

A still further object of the invention is to provide a wax base coating composition which will have desirable coating or covering characteristics, such as a high degree of elasticity, resistance to hardening, aging, changes in temperature and changes in humidity, and which can be modified by compounding with resins, asphalts, phenolic resins, alkyd resins and other synthetic resinous materials, copal gums, natural or synthetic fixed oils of the type disclosed in my aforesaid application Serial No. 748,665, and the like.

.Still another object of the invention is to provide a process for solubilizing gelatinized wax compounds in the presence of natural gums,

resins, asphalts and other natural materials thereby obtaining useful compounds of solubilized gels with the natural material.

still another object of the invention is to provide a process for solubilizing those insoluble waxes which are incapable of forming coherent useful compounds of such solubilized gels with synthetic resinous materials.

Still another object is to provide a process for solubilizing gelatinized wax compounds in such manner that the products can be dissolved in solvents and plasticizers for use in lacquers, cellulose derivatives and vinyl compounds, and can be dissolved readily in polymeriza'ble liquids *or solutions, such as styrene or the like to form stable solutions. v

Another object of the invention is to provide a process for increasing the swelling capacity of swollen or swelling waxes, to such an extent that they can be worked up in the usual thinners and varnish solvents.

These and otherobiects of the invention will be readily understood by reference to the following description:

I have discovered the metal soap-like reaction products, preferably formed by reacting a wax, fixed oil, fatty acid, a petroleum acid, a rosin acid, or mixture thereof with a compound of a metal capable of reaction with such waxes, oils, fatty acids, rosin acids, naphthenic acids or other organic compounds to form a corresponding wax soluble metal soap-like reaction product can be used to solubilize and influence the degree of swelling of waxes which are atleast partially insoluble and in a stage of swelling or are partially swollen, or which are completely swollen and in an insoluble condition.

I have discoveredfurther'that gelatinized or at least partially insoluble waxes can be 'solubilized by melting and compounding therewith certain metallic soap-like reaction products by subjecting the mixture to a melting temperature such that substantially the entire mass of the resulting composition is melted into the liquid stage thereby forming a soluble wax which is capable of forming a stable solution.

I have also discovered that the above-discovered process may be practiced with success by utilizing a metallic soap-like reaction product which is at least partially soluble and which is in a liquid state at the melting temperature of the above set forth process;

According to my invention, waxes, which are insoluble or at least partially insoluble, may be solubilized by melting and reacting therewith, at a temperature below the decomposition temperature of the resulting compound, a metal soap-like reaction product.

By insoluble I mean to include the characterization of any compound which is incapable of dissolving in a liquid to form a stable homogeneous mixture.

By gelatinized I mean to include any wax which may be at least partially insoluble and which is capable of increasing its volume when contacted by a solvent (swelling capacity). mean to include not only those gelatinized waxes which are film-forming but also those solidifications which are not capable of forming a film.

By solubilizin'g I mean to include the treatment of any insoluble or at least partially insoluble material to the extent that it will be capable of mixing with a liquid to form a stable, homogeneous'solution.

By metal soap-like reaction product I mean to include any alkali, alkaline-earth, or heavy metal compound of a complex organic acid or ester thereof, which is at least partially soluble in a Wax or fixed oil'.

By stable I mean to include any compound or {solution which will remain in a balanced Conan In addition, I w

' 6 iQ 9i m eeihility Wll h X 93 eedi-ly d tP pl t p Q? 32h? 'tip 9r pflik l P 9 PWQQQF it s ppss ble that t e met l $9 1.11? 'ee t e n s e Wel r er the e t n u WWW???- rd iwt bi th re eh y nt a 1. a e mb e m et of t e nv ntion i 1 25 te'a i' m' Q16 swabii' i l et 1 w Wa a f been eeelth'e fre 'asim eeetaii d the eee ical reaction. In preparing a, cent '1; gubstance, 5 like rgaetiqp products may be removed or he hat i a metal wepti e reeq e 'fiia et n e "b beag e with. boifl e fi 3% MW? w t th wee a 9 9? 1 WWW @5 9 ha $1491} 0 1" their acids or mix treatment does net interfere with the mature qt e i r m r e a h s 'n a s d ment m ies 'egm be .re ovee biffiltrijng, settli g fig wit 11 thereby renijovingth e Iiqui; e51 e tiriori's aterialfrpm the'eempouhq. "It" il the f hefs b, I ,h i f d' at the em pf .n 1 bmpo m with the nae a1 sro'euagk' 'i eac n'greduct may be ace 1p- "by Te eq'ndar mpese 'P usn may: i ee atin u p e i et i ta n ne su hur t n ietal 56 like rgpptidh'produpts} the probeee Q; i W P ptes eare el ith t Ermine 52 me a su h tlefsf'w eh c n b removed wh e: ueenie are l aeet b't n- V 'F'c'ir'pur see bf e'lari'ty', thevarious natural arm t f tt a i ee e "q nvl drdxyl a qqe 1' h t 115 th e ii e d o l rou s w ll e? t f ee at e -t e e t s w re h varibu natural aild jnthti fatty acids esterg of e x td e yl hswle eav l ss ha tl h rb ll e w l e e d t as the ax: type'etr'."' a rta n are? qllqw e exa l re a e of; em: R'Q f Q iS to an" ferrd proeese fer the preparation ofv a the ecmpdu d ne f h metafce qapi -lik e ce tat eubstance by com; h i mq 1551i he u l 'nt eti mate a 9? the ilQ cI aflyt 5W1 waii ti'beer fia tural'br smthetic materialg pt the ted t t e e mr Q 1 y e 9419 12?! w tbmetaleea ri ne me fi fii fi ts it tiqe 5f eel e e meta qxi e me a ea t awb in the fprrhxtidhdfatibnd "10g of u rflim ited swellmg". "It been mu at alk 11, mb-ear arid heayy metalgselected' :6 each of the 4e Wax and the COntfiCt subgtanee de en 'bfa partially" iri's o luble st ate "byfiatihg' ghee Iip -in degree sw'enm o h ubl i qi' f he ewi we; so 939 tezs wee gelatinized wax." 1 the elati ized V subtanlc'e. co nditidri to'be'readilj'swelle ,Qn lya mmrnaugr amount of contact substanc'l's required; where- H as a greater amount'isriecess'ary if the gelatinized Th9 following examples p w the ufig f Wax is in a cenditien W i h a r 9 readily materials of the wax type for preparatiqn b f the w'e 'ill f 'b' Q T he e h m a ee lse eon e eb tee e' t eqlu g elatihized waxes require a snr ialler pim qr mn' 5;, mgandsblubilizing'purpog 0f COnQt-at a e tfi i rea 9 5 (a) 50 parts of earnuba wax, a natural plant wise, certaiu \v' gesi which'haye been highly EB- c arbonate at :{ppu 10g angl ab oxge, the carlatinizeei by ontinued"heating, distillation 0'1 bdh ie a 5 3$ :5 m?! d? t w ng: etmg va c uurh treatme'ritlrefiuire ani'il r' efiam'd mt so was cbntinued until the reaeuon slowed dbwli, of Contact Substance! "W w ch he"? be which in this'instahce'eeeurred at abdlififimwcr altered orrriedti fied thejremdia lbf the 5 Upo n eoblirgg the ractibn predu'ctapfia'red as Example 1 gelatinized compdhe ts alslo require an irici'eased a Solid greenish hi orl ta f, ameunt e f c or'xtaet subs tane. stance was subsequently used for solub i l izatieu While it has been feufidthat an excess amount as illustrateq iri subeecjuent exam les? of ontact substariee" may be 'used for bbtjainihg y 50 p 'p of g gng w gj' natu animal certain "desired ehara cterist'ics," the "bropo'r'fiions x," er hatg Wm; t n parts 'e 1 'q'x q s86 forth ii the follewin g examples are preferred. Heatirig wasfcontmp until reactioh oc'urr e at "In af urther" embodiment of the "inve t on t about 100 0. Heatin'g'was then ontinud up t6 has beeri founci that the proeese of liquifyihg the 250 C. and a metal sqap -lik e contaet eub'stah ce geiatiiioue cbrhpdund with e'metal shah-like 1' was obtained, whi eh uppn ceoltrrg tqreqru temaet ioln broduet r riay be prbrhqted oraccelerated perature apeared as a dark brown s eh d matena}. by acidirig' a non-geiatinous 611, mm er other ma (e) 50 parts t montan wax, a atur al hgmte teriai which ie liqiiidatthe teri iperature of the wax, also referred to ae a s er i-mmera} wax, r lati d a he. meme 0; ting a a were heated We. Ha te elite tweet? WW1 were added-to the wax melt at around 110 C. Foaming occurred up to about 160 C., at which temperature the foaming subsided somewhat. Heating was continued with the occurrence of strong foam formation around 235 C. Heating was slowly continued up to about 275 C. Upon cooling to room temperature, 'a metal soap-like contact substance was obtained.

(d) In a modification of Example 1(a) above, -50 parts of montan wax were heated in a similar :manner with 20 parts lithium carbonate and heating was continued up to around 270 C., at which point the contact substance was obtained.

(6) 31 parts of polyethylene glycol-di-tri-ricinoleate, a synthetic wax-type substance, were heated with parts of cobalt acetate. Strong foaming developed around 100 C. and at around 150-C., a bluish liquid state was obtained and a slight wax-like form was observed in the area where the compound was in contact with the relatively cool air of the room. Heating was continued at around 200 C., the film was no longer observed and a uniform melt of brownish shade was obtained. Heating was continued somewhere slightly beyond 220 C; at which stage a semisolid contact substance was obtained upon coolmg.

In a similar manner, 45 parts candelilla wax were heated with 5 parts chromium carbonate. Foaming was most evident between 95 and 125 C., heating being continued up to around 280 C. The reaction product had an appearance similar to the product of Example a and was used subsequently for liquefying solid waxes and oils.

(g) 42 parts ouricuri wax were heated with 10 parts nickel sulphate and the reaction was carried up to about 280 C. A dark brown coloxalate.

under foaming during the heating which was ored reaction product was obtained and used in a later example for the liquefying process.

(h) 58 parts of Japan Wax were heated with 5 parts lithium hydroxide. After a quickly beginning foam formation, the heating was carried gradually up to around 275 C. Since some unreacted substance was observed, the melt was filtered through cheesecloth and a clear liquid was obtained which later hardened in cooling. The product was used as a contact substance in a later example for liquefying solid oil and wax.

(i) 39 parts of Japan wax were reacted in heating with 6 parts of silver nitrate. The reaction occurred around 220? C. The product remained cloudy, and was used in later examples as a contact substance.

(7') 20 parts Japan wax were heated with 6 parts aluminum sulfate. A liquid was formed initially and thereafter the natural wax portion of the compounded mixture combined with the aluminum salt to form a solid reaction product which remained solid up to 250 C. The remainder of the compounded mixture formed a liquid metal salt product which was then separated from the solid matter by filtration. Upon cooling, the liquid portion became a soft waxlike material which was subsequently used as a contact substance in the succeeding examples disclosing actual liquefaction.

(k) 20 parts of Japan wax were reacted under heating with 5 parts cupric oxalate. Heating was continued under occasional stirring up to and above 245 C. A greenish cloudy product was obtained which was used in a following example as a contact substance in liquefying at least partially insoluble substances.

8 (1) 27 parts of beeswax were reacted with 4.5 parts bismuth benzoate by heating and compounding for about 30 minutes up to around 250 C. A light yellowish brown reaction prodnot was obtained.

(m) 25 parts beeswax were heated and reacted with 5 parts manganese oxalate, heating being continued up to about 270 C. A medium brown reaction product was obtained.

(n) 20 parts ouricuri wax were heated and reacted with 6 parts zinc benzoate uponheating up to around 255 C. A reddish dark brown product was obtained.

(0) 18 parts carnauba wax were heated and compounded with 3 parts basic aluminum acetate up to about 280 C. A brownish wax-like product was obtained.

(:0) 30 parts polyethylen-glycol di-tri-ricinoleate, a synthetic wax-type composition were heated and reacted with 5 parts chromium A brownish compound was formed continued up to around 275 C.

(q) 12 parts carnauba wax were heated and reacted with 2 parts magnesium carbonate and under foaming, a brownish compound was obtained. The heating was continued up to around (r) 5 parts candelilla wax were mixed with 15 parts China-wood oil and the mixture was heated and reacted with 4 parts magnesium carbonate up to 255 C. The reddish brown product was subsequently used as a contact substance.

(s) 17 parts of beeswax were reacted with 3 parts antimony trioxide under gradual heating and stirring up to about 270 C. A greyish brown contact substance was obtained.

(if) 42 parts liquid polyethylene glycol 400 ditri-ricinoleate were heated and compounded with 7 parts zinc formate. Heating was carried to about 260 C.

(u) 15 parts ouricuri wax were heated and reacted with 3 parts aluminum borate. Very strong foaming was observed initially but the reaction subsided and heating was discontinued around 270 C.

(v) 25 parts diethylene glycol monolaureate, a synthetic wax type composition, was heated with 5 parts cobalt acetate up to about 240 C;

for about 15 minutes.

Example 2 The following examples illustrate the utilization of the wax-type reaction products as formed by the methods set forth in the preceding examples, either alone or in a mixture with minor' amounts of oil-type reaction products as disclosed in the aforementioned application S. N;

748,665, for the solubilization of at least partiall insoluble oil-type materials.

' (a) This example discloses the solubilization of a natural oil gel with a contact substance derived from a natural wax made in accordance with the preceding example:

20 parts of gelatinized linseed oil, which was at least partially insoluble and incapable of forming a stable solution with solvents such as petroleum naphtha or coal tar solvents, were composition was capable of being completely dissolved in the usual solvents. Thus, in this instance, 1 part of the resulting composition was substantially completely dissolved in 1.5 parts of toluene. The dissolved solution was then filtered and stored. Following several days storage, the solution was further diluted with 2 additional parts toluene and subsequently with 2 parts VMP petroleum naphtha, thereby illustrating that other solvents can be used for the solution of the resulting composition. It is desired to point out that the aforementioned solvents are normally used for dissolving ungelatinized natura oils.

(b) This example illustrates the liquefaction or solubilization of a gelatinized natural oil by melting and compounding therewith a contact substance derived from a synthetic wax product.

40 parts of gelatinized soybean oil were heated with 20 parts of polyethylene glycol-di-triricinoleate contact substance as formed in the preceding Example 1(0). The melting and compounding was carried out as in Example 2(a) above until liquefaction and solubilization was obtained at around 215 C. and thereafter heating was continued to about 270 C. After cooling, the resultant composition was dissolved in a ratio of one part to two parts of toluene and a stable liquefaction was obtained in the form, of a true solution.

This example illustrates the solubilization of a solidnatural oil with a natural wax contact substance in the presence of a soluble oil.

Ten parts of solid linseed oil prepared (in accordance with the method described and claimed in my co-pending application Ser. No. 33,676) by treatment with a potentially, free, oxygen-yielding compound incapable of forming a metal soap, at a temperature sufficiently elevated to effect the release of the free oxygen; in this instance benzoyl peroxide. The resultant solidified linseed oil was insoluble in coal tar and petroleum solvents. The ten parts solid linseed oil were heated with 5 parts of a shellac wax-type contact substance prepared in accordance with Example -1(b) above in the presence of parts of soluble bodied linseed oil known commercially as type Z-2. The soluble oil was added as a Wetting agent in order to increase the effect of the contact substance on the dry solid linseed oil. The mixture was compounded and heated until liquefaction occurred at around 250 to 265 C. The product was then thinned in a one to one ratio with petroleum naphtha and was further diluted by adding one part toluene to 5 parts of the naphtha solution. A stable soluble solution resulted. It will be apparent that the liquefaction may be accelerated by reducing the particle size of the solid linseed oil, as by breaking up the initial solid material into small chunks and particles.

"(d) This example illustrates the liquefaction of an at least partially insoluble gel of a synthetic oil with a wax-type contact substance. '12 parts gelled dehydrated castor oil, known commercially as Castung oil 103, were heated and compounded with 5 parts of the contact substance produced in Example 1(0) above from a synthetic wax. Liquefaction was reached at about 240 C. and the compound was further heated to about 265 C. and was thereafter dissolved in-a one to one ratio with a xylene solwent.

iii

(e) A similar effect as in the preceding example was obtained from gelled dehydrated castor oil by heating and compounding 10- parts of this gel with two parts of a natural lignite wax-type contact substance as produced in Example T.(c). Liquefaction was obtained at around 240 C. and heating was continued to about 270 C. The resulting composition was dissolved in about 20 parts of a hydrated solvent known commercially as Dekalin.

(f) This example illustrates the liquefaction of a solid modified polyhydroxyl alcohol fatty acid and phthalic anhydride ester, which may be identified as a solidified at least partially insoluble alkyd resin. 20 parts of a solid alkyd resin prepared by solidifying a commercial nondrying type oil-modified alkyd resin known commercially as Rezyl 925 by a compounding heat treatment with benzoyl peroxide, were heated with 10 parts of montan wax typesubstance as prepared in Example 1(a) above. The compounding and heating was performed in the presence of 6 parts soybean oil, liquefication being obtained around 235 C., and heating continuedup to around 280 C. The resulting composition was completely dissolved in equal parts toluene.

(g) This example illustrates the liquefaction of an at least partially insoluble oil gel with a mixture of contact substances, one being derived from an oil and the other being derived from a wax.

50 parts gelatinized perilla oil were liquefied by heating and compounding with a mixture of 5 parts contact substance obtained by reacting 93 parts linseed oil and 5 parts lead acetate together with 3 parts of the wax-type contact substance of Example 1(a) above. Liquefaction was obtained at around 225 C. and heating was continued at around 275 C. The product was substantially completely dissolved in about 1 /2 parts benzol.

(h) 12 parts heat-gelled linseed oil, which was partially insoluble and incapable of forming a stable solution with solvents, were resolubilized by heating and compounding with 4 parts of the contact substance obtained from Japan wax and aluminum sulfate as described in preceding Example 1(9'). The liquefied substance obtained at around 270 C. was of a relatively light color. It was completely diluted with 20 parts toluene. An application on a steel panel pro- .duced a resistant and glossy coating on baking at C. for 45 minutes.

(i) 18 parts of a gelled dehydrated castor oil, which was partially insoluble and incapable of forming a stable solution, were reliquefied by heating and compounding with 10 parts of the metal soap-like reaction product produced in preceding 'Exa-mple 1(k) from Japan wax and cupric oxalate. Liquefaction was obtained at around 260 C. and the product was completely thinned with 20 par-ts tetra-hydro-naphthalene 1 1 oil were liquefied by heating and compounding with 25 parts of the metal soap-like reaction product of Japan wax and silver nitrate described in Example. 1(z'). Liquefaction was obtained at around 260 C. and heating was continued up to 300 C. The product was uniformly thinned in a 1:1 ratio in toluene.

(Z) In a similar manner, 10 parts of solid olive oil, produced by reacting olive oil with 9% t-butyl perbenzoate'in'the method as described in Example c, were liquefied by heating and compounding with the metal soap-like reaction product obtained from heating candelilla wax with chromium carbonate (see Example 1(f)).

(m) 10 parts solid cod-liver oil, produced by heating and compounding twice with 7% ditertiary-butyl-diperphthalate, were liquefied by heating and compounding with 8 parts of the metal soap-like reaction product of Example 1(g) (heating ouricuri Wax with nickel sulfate). The liquefaction proceeded as described above in Example 7. r V

(n) 3.5 parts of an insoluble substance, obtained from China-wood oil by mixing it with about 0.5% anhydrous ferric chloride and holding it at around 50 C. for 24 hours, were reliquefied by heating and compounding with 8 parts of a contact substance prepared from ouricuri wax and zinc benzoate as set forth in Example 1. 3 parts of. a second type of commercial ironnaphthenate (6% Fe) was added to the mixture as an additional metal soap-like contact jsubstance; By heating the mixture under stirring'for 2 hours up to around 280-295 C. a dark melt was obtained which wa dissolved in 15 parts tetrahydronaphthalene (Tetralin). This solution was applied to a bonderized steel panel and dried over night in an oven at around 100 C. A coherent dry coating was obtained which had a Sward hardness of around 17.

15 parts of gelled linseed oil, which was at least partially insoluble in varnish solvents, like toluene, were reliquefied by heating with 8 parts of a greyish brown contact substance obtained from reacting up to around 270 C. 17 parts of beeswax with 3 parts of antimony trioxide. The liquefaction of the gelled oil with this contact substance was completed at around 265 C. and the product was thinned with toluene in the proportion of 1:1. A greenish solution was obtained which on cooling had a slightly cloudy appearance.

(p) 9 parts of at least partially insoluble and gelled solid linseed oil obtained in accordance with Example 1 were reliquefied by heating with 6'parts of a wax-type contact substance in the presence of 4 parts heat-break-stabilized linseed oil. The wax-type contact substance was prepared by heating 12 parts carnauba wax with 2 parts magnesium carbonate up to about 245 C. The liquefaction was completed at around 290 C. and the fused substance wa thinned with 20 parts of a hydrated solvent, tetrahydronaphthalene.

. (q) 12 parts of gelled linseed oil were reliquefied by fusing together (up to around 275 C.)

V with 7 parts of a wax-type contact substance at around 275 C. The liquefaction was thinned with equal parts toluene. The wax-type substance was prepared by heating and reacting 27 parts beeswax with 4.5 parts bismuth benzoate' heating beingcontinued up to around 250 C. A light yellowish brown substance was obtained'which served as a contact ubstance in.

this example. a r

(r) 10 parts synthetic oil, commercial sorbitolsoybean-fatty acid-ester oil, which had been at least partially insolubilized by heating and compounding with a free oxygen releasin catalyst (see Example 1), and which had been freed from it soluble oil components by'heating with benzol followed by drying, were reliquefied by heating 7 to about 280-285 C. with 5 parts of a wax-type contact substance. Thewax-type contact substance was produced by heating'up to' 270 C. and reacting 25 parts beeswax with 5 parts manganese oxalate. As a wetting agent, 1.5 parts of a liquid synthetic wa polyethylene glycol-400- di-tri-ricinoleate were added to the mixture during compound heating. The resulting liquefaction was diluted with solvent naphtha inthe proportion of 1 part non-volatile substance with 1.5 parts volatile matter.

(s) This example illustrates reliquefying a joint insolubilization or solidification product obtained ,from reacting 26 g. linseed on (type bodied oil Z-2) and 52 g. monostyrene under heating with 7 g. of a free oxygen releasing catalyst, t-butyl perbenzoate. The reaction was observed at around 145 C. and 51.5 g. solids were obtained. These solids would not dissolve in hot and drying it around 100 C. over night, a co-' herent film formation was obtained. Liquefaction occurred upon heating at 250 C. for about 70 minutes and stopping the heating at 270C.

(1) 8 parts heat-gelled long-oil alkyd gel, prepared by heatin '18 parts of a commercial longoil alkyd (Glyptal 2475), in'an open vessel at around 280-300 C. until a, strong gel had been formed, were liquefied by heating and reacting with 14'parts of a metal soap-like contact substance prepared by heating 42 part polyethylene glycol 400 di-tri-ricinoleate with 7 parts zinc formiate; Liquefaction of the gel was accomplished at around 270 C. The product was readily dissolved in equal parts benzol.

(u) 11 parts of a partially solidified, partially gelled and at least partially insoluble long-oil alkyd product was prepared by heat reacting a long-oil plastic alkyd (Aroplaz 1085) in the presence of.5-10% t-butyl hydroperoxide. The

7 product was liquefied by heating with 14 parts of the contact substance used in the previous example. 'The product was liquefied around 260 C. and was readily soluble in VMP petroleum naphtha.

(v) 15 parts of the same at least partially insoluble long-oil alkyd were liquefied by'heating and compounding with 6 parts of the contact substance prepared as in Example 1 by heating 25 parts of beeswax with 5' parts manganese oxalate up to about 270 C. Liquefaction was accomplished at around 250 C. and was completed around 2s5-275 'C. The product was dissolved in equal parts toluene. V

(w) 15 parts of solidified, incoherent sub stance which was at least partially insoluble in varnish solvents like benzol, petroleum solvents, hydrated solvents, etc., was produced by heatwith "3 parts aluminum bor ate as set forth in Example l. Liquefaction was f cornpleted around 20 3. the product was dis'solyedin e'dual parts tetrahydronaphthalen'e (Tetralin).

(a 1 6 parts of gelled and at least nartially insoluble linseed oil were resolubilized by heating and compounding with 10 parts of a conta'ct's'ub- "stance produced from 2 5'parts di 'ethylene glycol nonolaureate, synthetic wax ftype composition, and '5 parts cobalt acetate as in Example '1 '('v). The resolubilization "occurred at around 260? C.

and heating was continued up to about 275 C.

Thejjrodujc twascornbletely dissolved in narts solvent naphtha.

sample 3 T e fonoiiv'ing examples illustrate the resolubiliz'at'ion of at least partially in'soliibilized waxes and g'lled wax derivate's by of Conta t substances driyed from natural and synthetic "oil's 'inaccor'dance with the aforementioned applicat'ion s. N. 748,665. H y l a) 10 parts of partially insolubiliz'ed carnauba wax, -a natural p1ant were liquefied by heatingand "comnounding with ten rfarts of a c'ontact substance obtained by compounding 93 parts linseed oil with 1.5 parts cobalt acetate at a temperature somewhat above 200 C. The carnauba wax and the linseed oil type contact substance were heated and compounded, liquefactionoccuriing at around 240 C. Heating was continued up to about 280 C. and the product was thereafter dissolved in two parts VMP petroleum naphtha, thereby resulting in "a stable state of "solution. The resulting solution was "applied to a bond'er'ized steel panel, dried by baking at 120 *C. for minutes'and then aged for 24 hours at C. A dry film coating was obtained on the steel panel.

In "another application, parts of the product solution was combined with 48 parts of a paste consisting of 20 parts lead form-ate, 10 parts redglead, 4 parts zincoxide, 11 parts linseed oil (type 2-2) and 3 parts VMP petroleum naphtha. The resulting paint compound was applied to a steel panel and baked and aged as inthe case of the "preceding example. film had a sward hardness of 6.

b) 10 parts of at least partially insoluble animal waig; namely, spermaceti wax, were lique fied by heating and compounding with 10 parts offacontact substance obtained by melting and compounding 50 parts of a sorbitol-soybean fatty acid ester wit lv. parts manganese carbonateat about 290 0. The nartiallysolidifiedsperma'ceti wax and the contact substance were heated and The resulting comnoundegl to about 2 20 C. until :the reaction sub i f d d a u id qu dt'a t ne The resulting composition was substantially compltly dissolved equal barts beniol. l

I (c) 10 parts of at least partially insolubili'zed "mon es wax, a natural lignite wax, were liquefied by heating and compounding with Q parser linseedoil type contact substance as used EX- am l'e' 3(a) aboye In order to increase the g papaeityorthe contact sub tance on the e011 ifi'ed mesa-a wax, 1 0 eas toluene were eeded. as heating was ebntifi'ua the "sweet "C. The resulting composition was diluted with 15 parts xylene. V} v (d1 16 parts oi an at least partially insolubiliie'd "synthetic wax; namely, polyethylene glycol-dietri-ricinoleate, was resolubilize d by heating and compounding with an oil-type "Contact substance gob'tained by compounding and heating parts of linseed oil and 2 parts iron oxide, as set forth in the aforementioned co pending anplication S, N. 7{lS,665. The insoluble synthetic was; and "contact "substance were heated and compounded. upto a temperature of about 240? C.

which time liquelaction was obtained. eatall; was continued to 250? C. and the resulting composition was then thinned with 2 parts h 'e t (a), 10 parts partially insoluble 'beeswagwere lihiiefied by heating and compounding with 9 parts 'o ifla contact substance obtained frofn reacting 93 parts of soybean, oil with spam lead acetate at about 240 C. The compounds were heated under stirring toabout 250C. whereupon uniform liquid state was obseriied. Heating was continued to about 270 C. and the product uniformly thinned with a mixture of 10 parts solvent naphtha and '10 parts toluene. M (f) 10 parts partially insoluble oarna'uba wax were liquefied after ni'oisting with 10 parts "of a yolatile solvent, in this case Xylene, by heating and compounding with 8.5 parts of a'contact substa'aef (obtained. from reacting 40 parts, soybean oil with 6 parts nickel sulfate gradually up to 250C. and above) In the liquefabtiomproc'ess, the llduid state was observed at around 260 C. Heating was continued up to 290 C. anclthe b cduct was uniformly thinned with 20 parts to uene. V g V (g) 10 parts of at least parti'allyinsolubl'e solyent purified Japan wai: were 'reliquefiedbyheatmg with 20 bartsbfb contact substance obtained from heating 30 parts or dehydrated caste;- e11 '9 parts zinc formiate uio to around*250 to 269 C. whereby a light yellowish brown bidd- "uct was obtained. The mixture of the was; and the prepared contact substance was heated to around 285 C. under stirring. The liquefied reaction product was completely dissolved in 50 parts Xylene and a true solution was obtained.

(It) "8 narts of partially insoluble carnauba wax, which had been riurified three times by boiling with toluene followed by drying at C. for 3 days, were reli'qu'efied'by heating and temiabund ng them u to 310 C with lobarts of a g enish colored contact: substance obtained by heating 25 parts "commercial lard oil ('X-ZQB) iiritl '6 parts jcopiier 'okalat'e up to around 230 Thegliquefactionof the ca rnauba wan was "c'ompl'leltely dissolved in 25 parts benaol.

(2') Beeswax, obtained from reacting 50 parts elude beeswax under heating with S3 parts "tbutyl ii-erbenz oat'e and burifi'edby heating with 500 parts toluene and by filtering on the un- "disjb veu at least 'partially insoluble solid wax the toluene solution and dried over night at 100 was used in this example. The treated 'b'esjwa cdo's not nielt at temperatures up to about 309 [o But it wasmade fusible by heating and compounding up to 240? C.,6;15arts of this wax with 10. parts of a Contact substance "derived from Heating 10 partso f teaseed Oil with 15 3.5 part lithium mono-hydroxide. Under very strong foaming, a reddish brown compound was formed which remained liquid under heating and was decanted from a small residue of unliquefied crystalline substance. The resulting contact substance and the prepared beeswax were-heated under stirring up to 295 C. and formed a fused, liquid compound.

In a similar manner, 6 parts of the same prepared beeswax were fused into a liquid state by heating with 15 parts of another contact substance derived from heating 20 parts soybean oil ,With parts silver nitrate up to around 290 C. The contact substance was dark and cloudy in appearance.

(7') 8 parts of at least partially insoluble carnauba wax were fused and liquefied by heating and compounding with parts of a contact substance obtained from heating 26 parts soybean oil with 5 parts antimony oxide up to 280 C. A slightly yellow liquefaction was obtained. (k) 10 parts of at least partially insoluble V beeswax were liquefied by heating with 13 parts of a contact substance obtained from heating and compounding 23 parts cod-liver oil with 4 parts bismuth benzoate up to about 260 C. This contact substance was a dark brown material which showed some sedimentation of unreacted bismuth benzoate. Liquefaction was obtained on heating the prepared wax and the contact substance up to 295 C. under stirring. The resulting solution in equal parts xylene appeared as a greenish brown compound.

(Z). 4 parts at least partially insoluble ouricuri wax were liquefied by heating and compounding .with 6 parts of a contact substance obtained from heating parts menhaden fish oil with 4.5 parts chromic acetate up to around 255 C. This contact substance had a blueish brown color and showed that some unused surplus of metal salt remained undissolved. The wax was liquefied with this contact substance on heating and compounding at around 275285 C. The resulting liquefaction was dissolved in equal parts benzol.

(m) 10 parts of the same contact substance as in the preceding example were used for liquefying 8 parts at least partially solidified polyethylene glycol-di-tri-ricinoleate. The liquefaction was obtained at around 270 C. The product was thinned with equal parts xylene to form a true solution.

(n) 8 parts at least partially insoluble beeswax were liquefied by heating with 12 parts of a contact substance obtained from heating and compounding 20 parts cottonseed oil with a slight excess (3 parts) of aluminum hydroxide. At around 265 C., a light colored oil was decanted and used for the liquefaction of the wax. Liquefactionwas completed at around 285 C. and a 1 :1 toluene solution was made up, which Was light colored and wax-like in appearance after cooling.

(0) 9 parts of an at least partially insoluble ouricuri wax were reliquefied by heating and compounding with 10 parts of a contact substance produced by reacting 12 parts of a synethylene glycoldi-tri-ricinoleate were liquefied by using a metal soap-like contact substance de' rived from a synthetic fatty acid-ester of a resinous polyhydroxyl alcohol (the commercial esterification of dehydrated castor oil with Epon resin, which is a resinous polynydroxyl alcohol). 45 parts. of this synthetic oil-typeester were heated with 10 parts manganeous oxalate up to 275-280 C. A very tough and light colored product was obtained, which was used as the contact substance: 5 parts of the treated synthetic waxlike substance, 8 parts of the contact substance and 5 parts ofthe initial liquid synthetic wax likesubstance, the latter being added as a wetting agent, were heated and compounded up to'about 280 C. A liquefied, uniform product was obtained which was dissolved in equal parts xylene.

The resulting solution produced a coherent film when baked onto a steel panel.

(q) 12 parts at least partially insoluble ouricuri wax, obtained by reacting ouricuri wax with about 8-11% t-butyl perbenzoate under heating and compounding up to around 175 C. and followed by solvent extraction of the residual soluble matter with benzol, were solubilized by heating and compounding with 16 parts contact substance produced from beeswax and manganese oxalate as described in Example 1. Liquefaction was obtained at around 280 C. and the product was readily dissolved in equal parts toluene- (1') 7 parts of the same ouricuri wax were liquefied by heating with 7 parts of a contact substance produced from ouricuri wax and zinc benzoate according to Example 1. The liquefaction was performed up to around 285 C. and the product was directly dissolved-in one and onehalf parts xylene. I

(s) 8 parts of the same ouricuri wax were .liquefied by heating up to about 255 C. with 8 parts of a wax-type contact substance. The contact substance was obtained by heating and reacting 18 parts carnauba wax with 3 parts basic aluminum acetate. as described in Example 1. The liquefaction was thinned with equal parts xylene. After cooling, the solution had a soft wax-like appearance.

(t) 3 parts of an'at least partially solidified polyethylene glycol-400-di-tri-ricinoleate were moistened with 4 parts toluene and then compounded and heated up 'to 265 C; for about 40 minutes with 9 parts of a wax derived contact substance. This contact substance was produced'from'heatin and reacting 18 parts carnauba wax with 3 parts aluminum acetate up to about 280 C. At room-temperature it ap' peared as a wax-like coherent solid. The liquefaction of the solids was diluted with a hydrated solvent (comercial Hexalin) in the proportion of 1 part non-volatile'to 1 part volatile substance. On cooling,'a slightly waxy solution was obtained.

(u) 10 parts at leastpartially insoluble ouri- 'curi wax were liquefied by heating up to about 260 C. and reacting with 10 parts of a contact substance produced from heating 17 parts beeswax with 3 parts antimony trioxide up to about 270 C. The resulting liquefaction was thinned with equal parts benzpl and was further diluted With the same amount of VMP naphtha.

(v) 5.5 parts of the same ouricuri wax were liquefied by heating and reacting with 7 parts of a contact substance (under Example 1) produced from heating a mixture of candelilla wax and China-wood oil with magnesium carbonate, as in Example 1. The liquefaction was produced in the presence of 1.5 parts of soybean oil under 1 '17 heating up to. about 265 C. The compound was readily dissolved inone and one-halfparts xylene.

(w) 10 parts of the same ouricuri wajx were liquefied by heating and compounding with 8 parts of a contact substance produced by heating and reacting beeswax with manganese dxalate. The liquefaction was complete. ata'r'ound 280 C. and was readily dissolvedequal' parts in benzol.

(a2). 6 parts of at least partially solidified wool fat, a, wax-type animal product, weref 'l'iquefied byheati ng with 11 parts of a contactfsubstance produced from heating and reacting 12' parts carnauba wax with 2 partsmagnesium carbonate. To increase the initial contact between the two substances, 6 parts of a volatile solvent (xylene) were added. Heating and compoundin were continued up to about 270=280 Cfiand the pro duct was thinned with solvent naphtha infthe proportion of 1 part non-volatile matter with 2 parts solvent.

(y) 10 parts of solidified and at least partially insoluble polyethylene glycol-400-di-tri ricinole site were liquefied by heating with 9 parts of a contact substance (produced under Example 1 from the same material in its liquid soluble state and chromium oxalate). The wetting of the solids was facilitated by adding at the start 3 parts volatile solvent (xylene) and theliquefactionwas completed at around 250 C; The product was readily dissolved in equal parts toluene.

(z) The preceding example was repeated with a contact substance produced from the reaction product of 57' parts of the liquid synthetic wax with 10 parts bismuth benzoate, and similar resultswere obtained.

(ac) 3.5 parts at least partially insolublebees wax, as used in earlier examples, were solubilized by heating and compounding in the resence of 1' part liquid soybean oil with 7' parts ofa contactsubstance. This contact substance wasprofduced by heatin and reacting 20 parts of a polyhydroxyl alcohol fatty acid phthalicacid-ester compound; that is anoil-modified alkyd (commercial Rezyl 310-5), with 3 parts aluminumborate until foaming subsided at around 255 C. A light'brown reaction product was obtained:

, (bb) 3.5 parts of'the same beeswax wasliq'ue had in the presence of 1 part soybeanoil byheating and compounding with 7 parts of said con.- tactsubstance until liquefaction was obtained at around 250 C; The product was thinnediwith 1.4 parts hydrated solvent (commercial HexalinL (cc) 10 parts of a solidified polyethylene glycol-. 1OO-di-tri-ricinolate were liquefied with 10 parts of a contact substance produced from a long-oil-modified alkyd (commercial GIyptaI 24175), by reacting and compounding parts thereof with. 2.5. parts chromium carbonate upto 27.0 230" C; Theliquefaction of the solid syn} thetic wax was completed around 255 0., heating being continued up to 280 C. The product was; dissolved in: equal parts benzol. A light colored solutionwas obtained. I

(dd) 8 parts treated ouricuri wax, as used: in previous examples, were liquefied by heating and reacting with-,8 parts of a contact SllbStQIlCCFPIGr pared from a plastic-type, long-oil modified lkyd (commercial Aroplaz 1085 plastic). The contact substance was prepared by heating and compounding 54 parts of this alkyd with 10 parts leadacdtateupr o 260 C. and a lightabrownish product wasrobtained. which; was f a resin-like .anpearanceat. room temperature. Liquefaction of the wax was completed around 270 C. and

is the product was readily dissolved in equal parts VMP petroleum solvent.

Example 4 The following examples exemplify the resolubilization of at least partially insoluble waxes by heating and compounding therewitl'r contact substances of the wax-type prepared in accordance with Example 1 above.

(a) 10 parts of an at least partially insolubilized spermaceti wax, a natural wax, was used in the crude form in which it contained a gelled, partially solidified portion. The contact substance used in this instance was of the shellac wax type prepared in accordance with Example 1(b). above. To intensify the solubilizing reaction, 10 parts of a wetting substance, in this instance, a. synthetic oil, namely, synthetic sorbitel-linseed fatty acid esterification product, known commercially as Atlas oil G 8'75 was used. Liquefaction was obtained at around 250 C. The resulting composition was thinned with 1.5 parts toluene solvent.

(b) 50 parts of at least partially solidified insoluble natural wax, spermaceti wax in this instance, was resolubilized with parts of a contact substance produced from a synthetic wax in accordance with Example 1, above. In this instance, the contact substance comprised a metal soap formed from polyethylene g1ycoldi-triricinoleate and cobalt acetate. Liquefaction of the solidified spermaceti wax with the synthetic contact substance was obtained at about 200 C. and the resulting composition was thinned with a. two part compounded solvent consisting: of half exylene and half petroleum naphtha- (c) 20 parts of solidified. and at least partially insoluble montan wax were resolubilized by heating and compounding with 10 parts of a contact substance produced as set forth in Example. 1(0), in. this instance, a montan wax type contact substance, The heating and compounding was continued under stirringup to about 300 C. atwhich time liquefaction occurred. The resulting com.- position was thinned with 40 parts benzol sol.- vent. A clear solution was obtained Whichupon application to a metal surface in the form of a steel panel gave a fiat and uniform coating upon drying. In a similar test with a cobalt metal soap contact substance of the montan type, a finished film coating on a steel panel wasexposed to mineral oil (Shell grade Diala. oil #15) and heated to between and C. It was observed that, the film was not attacked by the oil up to this temperature.

(d) 20 parts of an at least partially insolubilizedsynthetic wax; in this instance, diethylene glycol monorlaureate (known commercially as Glaurin (were liquefied by compounding and heating with 20 parts of a. contact substance derived from shellac wax and red lead oxide as set forth in Example 1(b) above; The liquefaction was carried out in the presence of: 1.0 parts of ,diethyleneglycol mono-laureate utilized as a wettingagent for increasing the contactbetween the solid and thecontact substance; Liquefaction occurred at about 250 C. The resulting composition, was thinned by adding 2.2.part's1of toluene solvent, the solvent being added after the liquefaction had been cooled to about the boilingtemperature of the solvent.

(c) This example exemplifiesthe liquefaction Of an atzleastpartially insoluble synthetic. wax with; a.c;ontact substance. derived; from a. syn:- thetic wax.

20 parts of solidified di-ethylene glycol monolaureate were liquefied by heating and compounding with 20 parts of a contact substance prepared in accordance with Example 1(e) above, in this instance, the reaction product of a poly-ethylene glycol-di-tri-ricinoleate and cobalt acetate. The solidified synthetic wax and the synthetic wax type contact substance were heated and compounded up to about 270 C. at which point the liquefaction was observed. The resulting composition was thinned in an equal amount of toluene solvent.

(7) This example exemplifies the liquefaction of an at least partially insoluble wax 'by utilization of mixture contact substances derived from an oil.

10 parts of insolubilized carnauba wax were resolubilized by heating and compounding with a mixture of 12 parts of contact substance obtained from the reaction product of 93 parts linseed oil and 2.5 parts iron oxide plus 6 parts of contact substance in the form of a reaction product obtained from 60 parts beeswax with 5 parts basic bismuth acetate, the latter having been prepared in accordance with Example 1(5) above. The liquefaction of the insoluble carnauba wax with the mixture of contact substances, consisting of both an oil type and a wax type, was accomplished at around 225 C. Heating was continued to about 250 C. and the resulting composition was diluted with 40 parts xylene solvent.

(g) 21 parts partially insolubilized Japan wax were liquefied by heating and compounding with 17 parts of a metal soap-like reaction product which has been produced by heating 58 parts Japan wax with 5 parts lithium hydroxide (Example 1(h)). Liquefaction occurred at around 250 C. and heating was continued to around 290 C. Upon cooling the product was completely diluted with 40 parts benzol.

(h) parts partially solidified beeswax were resolubilized by heating and compounding with a contact substance comprising 4 parts of the reaction product of the Example 1(9) (curicuri wax and nickel sulfate) and 3 parts of the reaction product from Example 1( (candelilla wax and chromium carbonate). The solubilizing reaction was completed around 280 C. and

the product was uniformly thinned with parts a of xylene.

(i) In another test, 10 parts solidified, partially insoluble montan wax were reliquefied by heating and compounding with 9 parts of a metal soap-like reaction product obtained from-heating 39 parts of Japan wax with 6 parts silver nitrate (Example 1(i) Liquefaction was observed around 245 C. Heating was continued to around 280 C. and the product was thinned in a 1:1 ratio with toluene.

(7') 15 parts of the solidified and at least partially insoluble montan wax were reliquefied by heating them with 12 parts of the metal soaplike reaction product of Example 10) (which consisted in reacting 45 parts of candelilla wax with 5 parts chromium carbonate). tion was obtained around and above 275 C. The product was diluted with parts of the hydrated solvent, namely a commercial Hexaline.

(k) 12 parts partially insolubilized synthetic Liquefacwax, in this instance polyethylene glycol ditri-ricinoleate, were liquefied 'by heating and compounding with 10 parts of a contact substance comprising the reaction product produced in Example 1(7') from Japan wax and aluminium sul- 20 fate. The liquefaction was obtained at around 255 C., and heating was continued to about 275 C. The product was uniformly thinned with 20 parts of xylene. (Z) 10 parts of an at least partially solidifie diethylene glycol monolaureate were liquified by heating and compounding with 8 parts of a contact substance produced from 25 parts diethylene glycol monolaureate, a synthetic wax type composition, and 5 parts cobalt acetate as in Example 1(1)). Liquefactionwas obtained after heating up toabout 255 C. and the product was completely thinned with equal parts benzol.

Example 5 The following examples exemplify the resolubilization of at least partially insoluble waxes by means of contact substances of the free acid ype.

(a) In exemplifying the use of a fatty acid, 6 parts solidified beeswax in its crude form were resolubilized by treatment with 3 parts fatty acid contact substance; namely, a commercial copper oleate. Liquefaction of the solidified beeswax with the fatty acid contact substance occurred around 220 C. The product was dissolved in 10 parts tetrahydronaphthalene. On cooling the product to room temperature, it thickened to a wax-like form, but was readily dissolved upon slight warming by thinning with about 10 additional parts solvent. I

(b) 5 parts solidified diglycol stearate, recovered after a solvent purification, were resolubilized with 10 parts commercial lead naphthenate containing about 24% lead. 4 parts of a volatile VMP naphtha which evaporated during the liquefaction heating were used as a wetting substance. The liquefaction was obtained at about 240 C. The product was dissolved in 15 parts'of toluene and remained liquid at room temperature.

(c) In this example, a naphthenate type substance, commercial cobalt naphthenate containing about 6% cobalt was used as a contact substance. 15 parts solidified, at least partially insoluble American montan wax was obtained by heating 54 parts thereof with a free-oxygen releasing catalyst comprising 7 parts tertiary butyl perbenzoate until solidification occurred at about 260 C. The 15 grams solid montan wax was heated and compounded with 13 parts of the cobalt naphthenate substance in addition to 7 grams mineral spirits being added as a volatile solvent wetting agent. The mineral spirits evaporated during heating and reaction was observed at about 130 C. Heating was continued and at around 230 C. all the solid montan wax appeared to have been solidified. Heating under stirring was continued to about 250 C. The resulting composition was dissolved in 60 parts benzol' and the solution thereof was applied on a steel panel in the form of a film which was baked at about 0., whereby a permanent film of considerable gloss was obtained.

v In a similar example, solidified montan wax was liquefied with a montan wax type contact substance and 'a film was prepared on a steel panel as in the preceding example. The film was tested for its resistance to mineral oil (Shell grade Diala oil 15 being used). It was noted that the film was not attacked by the oil' until the temperature exceeded 0., thus illustrating the film-forming characteristics of the re- 3 solubilized wax'formed in accordance with the present process from injtially solid insolu- 2. 6 wax.

, (d) In this. instance a rosin acid type con-.- tact substance was uti zed. h ntac s b= stance being prepared from 105.1 acid and manganese acetate to give a manganese resinate' pa s of at ast pa tial m'sclubiliz d hellac wax were reliquefied by heating with 5 parts manganese resinate in the pl'fis ce of 2.5 parts linseed oil used as a wetting substance. Liquefaction was obtained at about.230 Q. and, the product was dissolved in 2.0 parts xylene solvent.

(e) In this instance, a nickel, resinate contact substance was utilized. 5 arts f at least partially insolubilizedsolid camallba wax in its crude form were resolubilized by heating with a m ture of 3. pa s ickel es na c con ct substance plus 1.5 parts of a, shellac wax-red lead c tact s bs n a Ob a ne n Exam le above. The solid carnaubawax and the mixture of the. nickel resinate. and shellac wax contact substances were heated, and compounded the presence of 2 parts corn oil used as a wetting substance. Liquefaction occurred around 245 C. and the product was dissolved in 15 parts toluene solvent.

(f) 2.8 parts solidified carnauba wax were resolubilized by heating with 20 parts of a solution consisting of parts of calcium naphthenate (4% calcium) contact substance in 10 parts of VMP naphtha. The solvent used. as a wetting substance evaporatedduring the heating and at about 225 C. liquefaction was obtained. The reaction product was dissolved in 10 parts toluene.

(g) In another test, the. liquefaction product of a solidified montan wax, obtained by treatment with cobalt naphthenate, was thinned with toluene in a 1:1 ratio and this solution was further diluted with 3 times the amountof a ketone solvent, in this case methyl-iso-butyl-ketone, which is a preferred solvent for various groups of coating materials. A clear solution was obtained which remained stable during 2 weeks storage at room temperature.

In another test, 5 parts solidified montan wax was mixed with 20. parts solid linseed oil as described in Example 2 (c), and this mixture was liquefied by heating and compounding with 30 parts of a commercial naphthcnate, in this case lead naphthenate (24% lead). Again the reaction product was thinned with 25 parts toluene. Afterwards the resulting solution was further diluted with 40 parts methyl-iso-butyl ketone and a stable, clear solution was obtained.

(h) 5 parts of solidified and at least partially insoluble beeswax were moistened with 2 parts toluene. As a contact substance, a, mixture of 5 parts commercial calcium naphthenate solution (5% Ca) and '7 parts commercial zinc naphthenate solution (8% Zn) werev added. The compound was heated up to about. 275 C. for about 45 minutes and a fusedmass wasobtained. This mass was dissolved in 20 parts tricresylphosphate. On cooling, a soft, waxy soluble substance was obtained.

(2') 18 parts of at least partially solidified and insolubilized and non-fusable. beeswax were liquefied by heating and compounding with 7 parts non-volatile cobalt, octoic metal soap contact substance and 13 parts volatile matter. To facilitate the wetting 7 parts of toluene were added. In this instance, commercial cobalt oowith 35% nonvolatile matter was used. Lique 22 faction of the solids was observed at around 275 C. and heating was discontinued at around 295 C. The product was dissolved in 25 parts toluene and a clear blue solution was obtained. This solution was clearly miscible in equal parts methyliso-butyl ketone. It was also clearly miscible with equal parts monostyrene.

(7') 16 parts gelled linseed oil were heated with 5.5 parts non-volatile cobalt-octoic. acid product in the presence of 10 parts volatile matter. The melting productwas held between 275 and 290 C. for. about 30 minutes until complete. liquefaction had been obtained. The resulting product was readily diluted with equal parts toluene. The l i fled wax from the preceding example was m xed in equal parts with this solution. of the liquefied oilgel and clear solutions were obtained.

Example 6 The following examples exemplify the resolu bilizationof a mixture of at least partially in soluble waxes and atleastpartially insoluble oils.

2.5 parts of a solidified wax substance; namely, polyethylene glycoldietriericinoleate wereadded to 3.5 parts of a solidified'oil product, namely, solidified sorbitol-linseed fatty. acid ester (known in the commercial form as Atlas oil G375). The mixture of the oil and wax insolublesubstances were solubilized byheating and compounding with 6.9 parts of a contact. substance consisting of a mixture. of 5.5. parts lithium napihthenate and 1.4 parts manganese naphthenate (6% Mn). The liquefaction was accomplished in the press encaof 1.5. parts soluble oil; in this. instance, the soluble sorbitol-linseed fatty acid estenwas used. Theliquefaction was. obtained at. about. 2.60. C. The. product was dissolved in a. mixture. of. 6, parts coal tar solvent, namely, toluene, and. 19, parts hydrated solvent, namely dekahydronaphthalene.

Example 7,

In order to exemplify the addition of pigments, colors. ,etc., in order to modify the process and products of the present invention, for use in the coating and impregnating arts, the solubilized product obtained in Example 3(a), namely, sol uble carnauba Wax, was pigmented with a pigment compound consisting of a mixture of'35 parts lead chromate, 17 parts red lead and 8 parts zinc oxide. This pigment was ground into the soluble carnauba wax until a normal'paint consistency was obtained and additional amounts of naphtha were added to enable the application of a uniform coating. The resulting paint composition was applied to panels which were dried for 45 minutes at C. and a dry uniform coat ing was obtained.

In accordance with the present invention it has been found that the solubilization of'at least partially soluble gelatinized natural or synthetic waxes or natural or synthetic oils, or combinationsthereof, maybe accomplished with waxtype or oil-type contact substances, or both, in the presenceof other materials such as asphalts, non-gelatinized oils, non-gelatinized waxes, res-. ins, gums, synthetic resinous; materials, such as phenolic. resins, alkyd resins and the like. It will alsobe understood that the final products of: the present invention may be supplemented or modiq fled. by. the addition of other oleo or resinous compounds, pigments, etc., for.improving their. application anduse inthe coating ,andimpreg, nating art Thu he phy i al propertie such as hardness, elasticity, color aflinity', acidre- 'sistance, drying conditions and the like may be improved by the aforementioned additions. In addition, the resulting compositions of the present invention may be hardened or solidified by the addition of vulcanizing or accelerating agents. Additionally, the compositions of the present invention may also be used as plasticizers for resinous compounds, lacquers such as cellulose lacquers, plastic compounds and the like.

It will be understood that the melting temperatures utilized to compound and solubilize the insoluble wax-type compounds or the insoluble oil-type compounds, or both, with either the oiltype or the wax-type contact substance, or both, is of such degree that substantially the entire mass of the resulting composition is melted into the liquid state without resulting in any decomposition. This melting temperature, as will be observed by reference to the foregoing examples, is generally in the neighborhood of 200 C. or above. In this respect, the required melting temperature is to be distinguished from the use of a lower temperature which is incapable of melting substantially the entire mass into a liquid state, or a higher temperature which would result in decomposition. Thus by virtue of the present invention, it is possible to form a soluble resulting composition which is capable of forming a stable solution, and one which is capable of being further diluted with the usual coal tar and petroleum solvents. Moreover, the solubilized final product is capable of being heated without gelatinization and is further capable of being regelatinized into a gel or other solid forms by utilization of a free oxygen releasing catalyst in the manner described in my pending application Ser. No. 33,676. Additionally, it should be pointed out that the resulting regelatinized and resolidified product resulting from reaction with a free-oxygen yielding catalyst may again be solubilized by means of the process of the present invention.

The present process has the further advantage that natural and synthetic wax compositions and natural and synthetic oil compositions may be decolorized and purified; that is, they may be freed of undesirable components in the solid state and in an at least partially solid state and can thereafter be resolubilized in accordance with the present invention for use in the coating and impregnating arts.

A further advantage resulting from the present invention is that hquefactions of the insoluble wax or oil compounds can be produced which are in the form of soluble solids at room temperatures prior to dilution or thinning with the usual solvents. Thus, these soluble solids can be kept easily, stored and shipped in a soluble solid form and can thereafter readily be dissolved in solvents and diluted for use in the arts.

Still another advantage of the present invention is that since the solubilized wax type or oil type products can be liquified in such manner that their melting point is considerably higher than that of the original soluble waxes and oils as commercially obtained in the natural synthetic state, and since such melting point can be modified by altering the ratio of the insoluble oil or wax to the contact substance, and further by adding varying amounts of preferred components as heretofore mentioned, it is thereby possible to produce impregnating and insulating compounds, paper coating and fabric treating compounds of a greater stability and usefulness than can be obtained from the use of the original oil or wax 24 compounds as they exist initially in their natural or synthetically produced state. i

A still further advantage of the present invention is that the at'least partially insoluble or solidified'oil or wax'compounds may be separated from such soluble'components as are contained therein,1such as bysolvent extraction, and it is therefore possible by the present invention to produce solubilized and liquified products which are practically free from such additional com-. pounds which make them incompatible with other waxes, oils or resins. In this manner it is possible to produce clear and soluble solutions which are free from undesired materials. 7 7

The wax or oil base compositionsof the present invention maybe used for the preparation of varnishes, lacquers, coatings, extrusions; coverings, modifiers'for resinous materials, impregnations for cloth and the like. They may also be used for producing electrical insulating materials. such as binding materials for fiber bindings, in addition to being used for heat and moisture insulating materials and as laminating compounds. v

I claim:

1. A'method of solubilizing an at least partially insoluble higher fatty acidester of an alcohol having from one totwo hydroxy groups which comprises melting and compounding with said ester a compound comprising a metal soap of a compound selected from the group consisting of higher fatty acid esters of a polyhydric alcohol, higher fatty acids, petroleum acids and rosin acids at a melting temperature below the decomposition temperature of the resulting composition and at such melting temperature that substantially the entiremass of the resulting compostiion is melted into the liquid stage, whereby to form a soluble ester reaction product capable of forming a stable solution.

2. The method set forth in claim 1 wherein the at least partially insoluble higher fatty acid-ester comprises such an ester of a dihydric alcohol.

3. The method set forth in claim 1 wherein the at least partially insoluble higher fatty acid ester comprises such an ester of a mono-hydric alcohol.

4. The method set forth in claim 1 wherein the at least partially insoluble higher fatty acid ester comprises a synthetically produced wax-like ester 1 of a higher fatty acid.

5. A method of solubilizing an at least partially insoluble natural Wax which comprises melting and compounding with said wax a compound comprising a metal soap of a compound selected from the group consisting of higher fatty acid esters of a polyhydric alcohol, higher fatty acids,

petroleum acids and rosin acids at a melting tem-' perature below the decomposition temperature of the resulting composition and at such melting temperature that substantially the entire mas of the resulting composition is melted into the liquid stage, whereby to form a soluble wax reaction product capable of forming a stable solution.

6. The method set forth in claim 5 wherein the at least partially insoluble natural wax comprises an animal wax.

7. The method set forth in claim 5 wherein the at least partially insoluble natural wax comprises a vegetable wax.

8. The method set forth in claim 5 wherein the at least partially insoluble natural wax comprises an insect wax.

9. A method of solubilizing an at least partially insoluble wax which comprises melting and a soluble wax reaction product capable of form- 10 ing a stable solution.

MAX KRONSTEIN.

26 REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Name Date Kronstein July 16, 1949 Number 

1. A METHOD OF SOLUBLIZING AN AT LEAST PARTIALLY INSOLUBLE HIGHER FATTER ACID ESTER OF AN ALCOHOL HAVING FROM ONE TO TWO HYDROXY GROUPS WHICH COMPRISES MELTING AND COMPOUNDING WITH SAID ESTER A COMPOUND COMPRISING A METAL SOAP OF A COMPOUND SELECTED FROM THE GROUP CONSISTING OF HIGHER FATTY ACID ESTERS OF A POLY-HYDRIC ALCOHOL, HIGHER FATTY ACIDS, PETROLEUM ACIDS AND ROSIN ACIDS AT A MELTING TEMPERATURE BELOW THE DECOMPOSITION TEMPERATURE OF THE RESULTING COMPOSITON AND AT SUCH MELTING TEMPERATURE THAT SUBSTANTIALLY THE ENTIRE MASS OF THE RESULTING COMPOSITION IS MELTED INTO THE LIQUID STAGE, WHEREBY TO FORM A SOLUBLE ESTER REACTION PRODUCT CAPABLE OF FORMING A STABLE SOLUTION. 